CN102686615B - Process for production of syndiotactic alpha-olefin polymer - Google Patents

Process for production of syndiotactic alpha-olefin polymer Download PDF

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CN102686615B
CN102686615B CN201080057971.XA CN201080057971A CN102686615B CN 102686615 B CN102686615 B CN 102686615B CN 201080057971 A CN201080057971 A CN 201080057971A CN 102686615 B CN102686615 B CN 102686615B
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olefin
alpha
carbonatoms
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zirconium dichloride
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CN102686615A (en
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山本昌由
雪田崇史
山下正洋
兼吉宽矛
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Abstract

Provided is a process by which a syndiotactic alpha-olefin polymer having a high racemic dyad fraction and a high molecular weight can be produced with excellent polymerization activity by means of a method that permits high-temperature polymerization. A process for the production of a syndiotactic a-olefin polymer by polymerizing a monomer component that comprises both at least one C3-10 alpha-olefin and a small amount of ethylene in the presence of an olefin polymerization catalyst which comprises (A) a transition metal compound represented by general formula [1] and (B) at least one compound selected from among (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the transition metal compound (A) to form an ion pair, and (b-3) an organoaluminum compound, characterized by satisfying the relationship: 0.001 <= PE/PO <= 0.030 [wherein PE and PO represent respectively the molar amounts of ethylene and C3-10 a-olefin which are fed into a polymerizer under the condition of polymerization temperature of 25 DEG C or higher].

Description

The manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer
Technical field
The present invention relates to the manufacture method of the syndiotaktisch isotactic alpha-olefin propylene series copolymer that uses the metallocene catalyst that comprises the transistion metal compound with ad hoc structure.
Background technology
The alpha-olefin that is 3～10 as polymerization carbonatoms, at the catalyzer of industrial manufacture olefin polymer, known have a Ziegler-Natta catalyst, particularly manufactures polyacrylic catalyzer as the propylene that is 3 for polymerization carbonatoms and used at world wide.This Ziegler-Natta catalyst is because not only generate the polypropylene of high molecular with high reactivity, and can highly control the arrangement of propylene, so the polypropylene taxis generating is high, therefore can obtain dystectic isotactic polyprophlene with high crystalline.On the other hand, because it is multiple that the avtive spot comprising in catalyzer exists, so can enumerate as problem points: with isotactic polyprophlene simultaneously by-product go out the atactic polypropylene(APP) of the irregular arrangement of propylene, and in the time of the alpha-olefin that copolymerization of ethylene and carbonatoms are 3～10, the ratio of the alpha-olefin comprising in polymer chain becomes inhomogeneous, and the composition of the multipolymer that its result obtains distributes and broadens.
In addition, since finding metallocene catalyst from 1980 by W.Kaminsky etc., alpha-olefin that metallocene catalyst is also 3～10 as polymerization carbonatoms gradually, used at the catalyzer of industrial manufacture olefin polymer.In the situation of metallocene catalyst, because be mostly single metal complex, so different from Ziegler-Natta catalyst, metallocene catalyst avtive spot is even, the ratio of the alpha-olefin comprising in the polymkeric substance that the alpha-olefin that is therefore 3～10 at copolymerization of ethylene and carbonatoms obtains becomes evenly, so by the advantage that can access the multipolymer that forms narrowly distributing, high-quality.In addition, by the dentate structure of conversion metal complex, just can highly control carbonatoms and be the arrangement of 3～10 alpha-olefin, for example, when the propylene that is 3 at polymerization carbonatoms is manufactured polypropylene, just there is following feature: not only can obtain equally with Ziegler-Natta catalyst highly isotactic polypropylene, and by-product atactic polypropylene(APP) not.
While using metallocene catalyst polymerisation propylene to manufacture isotactic polyprophlene, known hydrogenation in reactive system and be adjusted to desirable molecular weight.Report by hydrogenation and can improve catalyst activity, and illustrated that this is to react because of the state that propylene inserts with 2,1-the catalyzer kind stopping to be re-activated (non-patent literature 1) by hydrogen.On the other hand, because the polyacrylic molecular weight and molecular weight obtaining along with the increase of hydrogenation amount, so especially in the time that desirable molecular weight is high, the availability of hydrogenation is also limited, its range of application is restricted.
In addition, reported when in use metallocene catalyst is manufactured on propylene, copolymerization has the isotactic polymer (Atactic Polypropelene) of a small amount of ethene, along with increasing the ethene amount of adding in reactive system, catalyst activity improves (non-patent literature 2).Now, because comprise ethylene unit and polyacrylic melting point depression in the molecular chain of isotactic polyprophlene generating, so especially in the time that desirable thermotolerance is high, have the problem that ethene addition is restricted and other physical propertiess also change.Therefore, be conceived to add by this ethene the high reactivity producing, proposed to reduce the scheme (patent documentation 1) of ethene addition.Particularly, using non-crosslinked type, having in dentate in the propylene polymerization system of metallocene catalyst of at least a kind of 2-aryl indenes, if add a small amount of ethene (more than preferred about 2wt%), catalyst activity increases.In the open example of this report, comparison when not adding ethene, using two (2-(3,5-di-tert-butyl-phenyl) indenyl) zirconium dichloride is when to manufacture ethylene content be the Atactic Polypropelene of 1.9 % by mole, although active and molecular weight improves, the fusing point of polymkeric substance drops to 137 ℃ from 144 ℃.The tensile properties of the Atactic Polypropelene obtaining in addition, shows until high stretching is out of shape equably, is replied such elastomeric properties from the height stretching.,, in the time that desirable thermotolerance is high, do not eliminate the problem that ethene addition is restricted and other physical properties also changes.On the other hand, reported in 1989 and can manufacture the syndiotactic polyacrylic metallocene catalyst of the height that cannot be obtained by Ziegler-Natta catalyst (non-patent literature 3).If use with aikyiaiurnirsoxan beta the metallocene catalyst polymerisation propylene of IV group transition metal compound activation, just can obtain highly syndiotactic polypropylene, this IV group transition metal compound is to be cross-linked the isopropylidene (cyclopentadienyl) (9-fluorenyl) obtaining as dentate by carbon atom by cyclopentadiene and fluorenes.Syndiotactic structure is as follows, and the substituting group of combination on tertiary carbon (being methyl when propylene) has the relation in " racemize " of alternating direction mutually, the comparison of " meso " having with the isotactic structure of following expression.
Isotactic polyprophlene
Figure BDA00001784774300032
Syndiotactic polypropylenes
The relation of the racemize chain by adjacent connection keeps for a long time, just become the polymkeric substance of height syndiotactic structure, in above-mentioned report, to represent that the index that 4 continuous parts of racemize chain are occupied the racemize five unit composition ratio of ratio in all represents its degree.In report example, the highest racemize five unit composition ratio are 0.86, if be scaled simple racemize chain (racemize diad point rate), are 0.96 to be very high value.In addition, because highly syndiotactic polymkeric substance is crystallinity, racemize diad divides the proportional relation of fusing point (temperature of fusion) of rate and racemize five unit composition ratio and polymkeric substance, thus generally speaking highly syndiotactic polymkeric substance more show high-melting-point.
There is following report: by the substituent three-dimensional impact of this adjacent connection, when isotactic polyprophlene, take rotate spiral helicine 2 level structures of 1 week and form crystal with 3 molecule propylene, with respect to this, when syndiotactic polypropylenes, experience in the impact of the direction replacing or by its thermal history and stress by substituting group, can take stable crystalline structure on multiple energy such as helicoidal structure, planar zigzag structure, in addition, can reversibly phase transition between a part of crystalline structure (non-patent literature 4).Report has the difference of such crystalline structure also to have a significant impact the difference of polymer materials characteristic, and syndiotactic polypropylenes has thermal properties, physical properties, the mechanical properties with isotactic polyprophlene different characteristics.In addition, the difference of the material behavior that the difference of this syndiotactic structure and isotactic structure is brought also can be seen in other alpha-olefinic polymer, therefore requires effectively to manufacture the polymkeric substance of syndiotactic structure.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2002-505707 communique
Non-patent literature
Non-patent literature 1:Macromol., Chem., Rapid Commun., 1993,14,97
Non-patent literature 2:Polymer, 1989,30,1350
Non-patent literature 3:J.Am.Chem.Soc., 1988,110,6255
Non-patent literature 4:Macromolecules, 1993,26,5711
Summary of the invention
Invent problem to be solved
The present inventor carries out the result of deep investigation, find the catalyst for olefines polymerizing that comprises the crosslinked metallocene compound with ad hoc structure by use, alpha-olefin and a small amount of ethene that a kind of above carbonatoms is 3～10 are existed under polyreaction atmosphere with specific ratio, thereby polymerization activity improves, and the molecular weight of the syndiotaktisch isotactic alpha-olefin propylene series copolymer generating also improves, obtain the manufacture method of dystectic polymkeric substance, thereby completed the present invention.
For solving the method for problem
, the present invention is the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer, wherein, comprise the transistion metal compound shown in (A) following general formula ［ 1 ］ and (B) be selected from (b-1) Organoaluminoxy compound, (b-2) with the right compound of transistion metal compound (A) reacting forming ion with (b-3) under the existence of the catalyst for olefines polymerizing of at least a kind of compound in organo-aluminium compound, when the monomer of the alpha-olefin that under the condition at polymerization temperature more than 25 ℃, aggregate packet is 3～10 containing more than a kind carbonatoms and on a small quantity ethene, the ethene mole number of supplying with polymerizer is made as to P e, the alpha-olefin mole number that is 3～10 by carbonatoms is made as P otime, meet 0.001≤P e/ P o≤ 0030.
In general formula ［ 1 ］, R 1, R 2, R 3and R 44 groups be selected from hydrogen atom, alkyl and containing silica-based, identical or different respectively, R 1and R 2do not mutually combine and form ring, R 3and R 4do not mutually combine and form ring.R 5and R 6for being selected from alkyl that hydrogen atom, carbonatoms are 2～20 and containing atom or substituting group in silica-based, mutually identical or different.M is selected from titanium atom, zirconium atom and hafnium atom, and Q represents that halogen atom, alkyl, carbonatoms are neutral conjugated diolefine below 10 or non-conjugated diene, anion binding base or can be with the neutral dentate of lone-pair electron coordination.J represents 1～4 integer, and j is 2 when above, and multiple Q are mutually identical or different.］
The effect of invention
Than the manufacture method that does not comprise a small amount of ethene, the manufacture method of olefin polymer of the present invention, the molecular weight of polymerization activity and alpha-olefinic polymer improves, and the syndiotaktisch isotactic alpha-olefin propylene series copolymer generating is maintaining high-melting-point.
In addition, if use the olefin polymerization catalysis that comprises transistion metal compound of the present invention, in the polymerization at industrial possible temperature, also can manufacture the syndiotaktisch isotactic alpha-olefin propylene series copolymer of high molecular.
Embodiment
Below, in the present invention, about transistion metal compound (A), organometallic compound (B), the catalyst for olefines polymerizing that comprises these two kinds of compositions, under this catalyst for olefines polymerizing exists the method for polymerizable alkenyl hydro carbons, the optimum way of explanation for carrying out an invention in turn.
< transistion metal compound composition (A) >
Transistion metal compound composition (A) is made up of the transistion metal compound shown in following general formula ［ 1 ］.Transistion metal compound (A) is crosslinked metallocene compound.The mole number of the ethene of supplying with polymerizer is being made as to P e, the mole number of the alpha-olefin that is 3～10 by carbonatoms is made as P otime, meet 0.001≤P e/ P oin≤0.030 situation, the alpha-olefin that transistion metal compound composition (A) can be take high polymerization activity polymerization carbonatoms as 3～10.In addition, the alpha-olefin chain of the alpha-olefinic polymer obtaining, for height syndiotactic, balancedly meets high molecular and high-melting-point.
Figure BDA00001784774300061
In above-mentioned formula ［ 1 ］, R 1, R 2, R 3and R 44 groups be selected from hydrogen atom, alkyl and containing silica-based, identical or different respectively, R 1and R 2do not mutually combine and form ring, R 3and R 4do not mutually combine and form ring.More preferably R 1and R 4for same atoms or identical group, R 2and R 3for same atoms or identical group, particularly preferably R 2and R 3for the tertiary butyl.
In addition, in above-mentioned formula ［ 1 ］, R 5and R 6for being selected from alkyl that hydrogen atom, carbonatoms are 2～20 and containing atom or substituting group in silica-based, mutually identical or different.More preferably R 5and R 6for the carbonatoms alkyl that is 6～20.
The alkyl that is 6～20 as carbonatoms, can enumerate the aryl of phenyl, naphthyl etc.; The alkylaryl of o-tolyl, a tolyl, p-methylphenyl, ethylphenyl, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, xylyl etc.; The chlorine aryl of Chloro-O-Phenyl, a chloro-phenyl-, rubigan, chloronaphthyl, methylnaphthyl etc.; O-bromophenyl, a bromophenyl, bromine aryl to bromophenyl, bromonaphthalene base etc.; The bromine alkylaryl of 2-bromomethylphenyl, xylylene bromide base etc.; Adjacent iodophenyl, an iodophenyl, iodine aryl to iodophenyl, iodine naphthyl etc.; The iodine alkylaryl of iodomethyl phenyl, diiodomethyl phenyl etc.; The aralkyl of benzyl, α-styroyl, β-styroyl, diphenyl methyl, naphthyl methyl, neophyl etc.; Between chlorobenzyl, p-chlorobenzyl, a bromobenzyl, to bromobenzyl, an iodine benzyl, benzyl halide to iodine benzyl etc. etc.
R 1and R 4be preferably hydrogen atom or carbonatoms and be 6～20 alkyl, the aryl that more preferably hydrogen atom or carbonatoms are 6～10, is particularly preferably hydrogen atom, phenyl, o-tolyl, a tolyl, p-methylphenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan.
R 5and R 6respectively identical or different, be preferably carbonatoms and be the aralkyl that 6～10 aryl or carbonatoms are 6～10, be particularly preferably phenyl, benzyl, a chloro-phenyl-, rubigan, a chlorobenzyl, p-chlorobenzyl.
M is titanium, zirconium or hafnium, is preferably zirconium or hafnium, is particularly preferably zirconium.
Q is selected from halogen atom, alkyl, anion binding base or can be with the atom in the neutral dentate of lone-pair electron coordination or group with identical or different combination.
As the object lesson of halogen atom, for fluorine, chlorine, bromine, iodine, as the object lesson of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1,1-dimethyl propyl, 2,2-dimethyl propyl, 1,1-diethyl propyl group, 1-ethyl-1-methyl-propyl, 1,1,2,2-tetramethyl-propyl group, sec-butyl, the tertiary butyl, 1,1-dimethylbutyl, 1,1,3-trimethylammonium butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl, s-cis-or s-trans-η 4-1,3-butadiene, s-cis-or s-trans-η 4-Isosorbide-5-Nitrae-phenylbenzene-1,3-butadiene, s-cis-or s-trans-η 4-3-methyl isophthalic acid, 3-pentadiene, s-cis-or s-trans-η 4-Isosorbide-5-Nitrae-dibenzyl-1,3-butadiene, s-cis-or s-trans-η 4-2,4-hexadiene, s-cis-or s-trans-η 4-1,3-pentadiene, s-cis-or s-trans-η 4-Isosorbide-5-Nitrae-xylyl-1,3-butadiene, s-cis-or s-trans-η 4-Isosorbide-5-Nitrae-bis-(trimethyl silyl)-1,3-butadiene etc.
As the object lesson of anion binding base, can enumerate the alkoxyl group of methoxyl group, tert.-butoxy, phenoxy group etc., the carboxylic acid ester groups of acetic ester, benzoic ether etc., the sulfonate group of methanesulfonates, tosylate etc. etc.As can be with the object lesson of the neutral dentate of lone-pair electron coordination, can enumerate the organo phosphorous compounds of trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine etc., or tetrahydrofuran (THF), diethyl ether, diox, 1, the ethers of 2-glycol dimethyl ether etc.
The preferred configuration of Q is the alkyl that halogen atom or carbonatoms are 1～5.
J is 1～4 integer, is preferably 2.
transistion metal compound (A) and illustration thereof
Below, illustrate the object lesson of the transistion metal compound (A) shown in above-mentioned general formula ［ 1 ］ in the present invention, but do not limit especially thus scope of the present invention.
As the object lesson of the transistion metal compound (A) shown in above-mentioned general formula ［ 1 ］ in the present invention, can enumerate dibenzyl methylene radical (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butyl fluorenyl) zirconium dichloride is ［ in addition also referred to as 1,3-phenylbenzene isopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butyl fluorenyl) zirconium dichloride.At the following another name that omits ］, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-(2, 4, 6-trimethylphenyl)-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-(3, 5-3,5-dimethylphenyl)-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-(4-aminomethyl phenyl)-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-dinaphthyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-(4-tert-butyl-phenyl)-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two phenethyl methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (benzhydryl) methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (cumyl) methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-o-tolyl methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two tolyl methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-p-tolyl methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (Chloro-O-Phenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (chlorphenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (o-bromophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (adjacent iodophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (iodophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (o-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethylphenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride,Two (o-chlorobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (chlorobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-chlorobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (adjacent bromobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (bromobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromobenzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (adjacent iodine benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (an iodine benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodine benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (adjacent methyl-benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (methyl-benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to methyl-benzyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (p-chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (p-chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (p-chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (rubigan) methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (rubigan) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (rubigan) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-p-tolyl methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride,Two (p-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-chlorobenzyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to methyl-benzyl) methylene (cyclopentadienyl group) (2, 7-di-o-tolyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-di-o-tolyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-(adjacent ethylphenyl)-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (n-pro-pyl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (isopropyl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (normal-butyl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (isobutyl group) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (sec-butyl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (tert-butyl group) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (n-eicosane base) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-(adjacent cyclohexyl phenyl)-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-(xenyl-2-yl)-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (2-naphthyl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-［ adjacent (2-phenanthryl) phenyl ］-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-(adjacent trimethyl silyl phenyl)-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ［ 2, 7-bis-(adjacent triphenyl silicyl phenyl)-3, 6-di-t-butyl fluorenyl ］ zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-diphenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride,Diphenyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-p-tolyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-chlorobenzyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to methyl-benzyl) methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-bis-trimethyl silyl fluorenyls) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-dicumyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-rubigan-3, 6-adamantyl fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diethyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diη-propyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diisopropyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-sec-butyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-t-butyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-octyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two-positive melissyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, phenylmethylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride,Di-p-tolyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-chlorobenzyl) methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to methyl-benzyl) methylene (cyclopentadienyl group) (2, 7-bis-p-trifluoromethyl phenyl-3, 6-di-t-butyl fluorenyl) zirconium dichloride and the zirconium atom of above-claimed cpd is substituted by hafnium atom, the compound of titanium atom or the chlorine atom of above-claimed cpd is substituted by methyl, the compound of benzyl or their combination etc., but be not limited to these.In addition, in hafnium atom, zirconium atom, titanium atom, be preferably zirconium atom.Above-claimed cpd both can use separately, also can combine two or more use.
the manufacture method of transistion metal compound (A)
The transistion metal compound (A) that used in the present invention can be manufactured by known method, and manufacture method is not particularly limited.As manufacture method, for example, can be manufactured by the method for the records such as TOHKEMY 2000-212194 communique, TOHKEMY 2004-168744 communique, TOHKEMY 2004-189666 communique, TOHKEMY 2004-161957 communique, TOHKEMY 2007-302854 communique, TOHKEMY 2007-302853 communique, WO01/027124 communique, Japanese Unexamined Patent Application Publication 2001-526730 communique, Japanese kokai publication hei 10-226694 communique.
optimal way supply with transistion metal compound (A) in the manufacture of olefin polymer time
Then the optimal way while, catalyst for producing (olefin polymerization catalysis) use using transistion metal compound used in the present invention (A) as olefin polymer being described.
< olefin polymerization catalysis >
Using above-mentioned transistion metal compound (A), when olefin polymerization catalysis uses, catalyzer comprises transistion metal compound (A) and organometallic compound (B).Wherein, organometallic compound (B) comprise be selected from following (b-1), (b-2) and (b-3) in a kind of above organometallic compound (B).
(b-1) Organoaluminoxy compound
(b-2) compound right with above-mentioned transistion metal compound (A) reacting forming ion
(b-3) organo-aluminium compound
Wherein, (b-1), (b-2) and (b-3) both can distinguish separately and to have used, also can combine two or more use.In addition, olefin polymerization catalysis can also comprise granular carrier (C), organic compound ingredient (D) as required.Below, illustrate each composition.
［ Organoaluminoxy compound (b-1) ］
As the Organoaluminoxy compound (b-1) using in the present invention, can directly use existing known aikyiaiurnirsoxan beta.Particularly, can enumerate the compound of following general formula ［ 2 ］ and/or following general formula ［ 3 ］ representative,
Figure BDA00001784774300121
(in above-mentioned general formula ［ 2 ］ and ［ 3 ］, R represents that carbonatoms is 1～10 alkyl, and n represents more than 2 integers.), particularly R is that methyl, n are more than 3, the compound that is preferably more than 10 is suitable as methylaluminoxane (MAO) utilization.In these alumina alkanes, can sneak into organo-aluminium compound.
In addition, as the Organoaluminoxy compound (b-1) using in the present invention, also can enumerate the such modification methylaluminoxane of following general formula ［ 4 ］ etc.
Figure BDA00001784774300131
(wherein, R represents that carbonatoms is 2～10 alkyl, and m, n represent more than 2 integers.）
This modification methylaluminoxane is used the aluminum alkyls preparation beyond trimethyl aluminium and trimethyl aluminium.The compound of above-mentioned formula ［ 4 ］ is like this commonly referred to as MMAO.Such MMAO can be with the method preparation of enumerating in No. US4960878 and No. US5041584.In addition, Tosoh-finechem company etc. also will be used trimethyl aluminium and triisobutyl aluminium compound preparation, that R is isobutyl-to carry out commercial production with the title of MMAO or TMAO.These MMAO have improved to the solvability of all kinds of SOLVENTS and the aikyiaiurnirsoxan beta of storage stability, and particularly, the MAO such from above-mentioned formula ［ 2 ］, ［ 3 ］ is different, but are dissolved in the aikyiaiurnirsoxan beta of aliphatic hydrocarbon or clicyclic hydrocarbon.
As the Organoaluminoxy compound (b-1) using in the present invention, also can enumerate the boracic Organoaluminoxy compound shown in following general formula ［ 5 ］.
Figure BDA00001784774300132
(in formula, R crepresent the alkyl that carbonatoms is 1～10.R dmutually identical or different, represent the alkyl that hydrogen atom, halogen atom or carbonatoms are 1～10.）
In addition, the Organoaluminoxy compound (b-1) of enumerating in above-mentioned general formula ［ 2 ］～［ 5 ］ both can use separately, also can mix two or more use.
［ compound (b-2) right with transistion metal compound (A) reacting forming ion ］
As the compound (b-2) (be below sometimes slightly called " ionic compound ") right with transistion metal compound (A) reacting forming ion, can be set forth in Lewis acid, ionic compound, boron compound and the carborane compound etc. in Japanese kokai publication hei 1-501950 communique, Japanese kokai publication hei 1-502036 communique, Japanese kokai publication hei 3-179005 communique, Japanese kokai publication hei 3-179006 communique, Japanese kokai publication hei 3-207703 communique, Japanese kokai publication hei 3-207704 communique, USP5321106 communique etc., recorded.Can also enumerate heteropoly compound and with polyvoltine compound.
In the present invention, the ionic compound (b-2) preferably adopting is the borate compound shown in following general formula ［ 6 ］.
Figure BDA00001784774300141
(in formula, as R e+, can enumerate H +, carbocation, oxygen positively charged ion, ammonium cation, phosphonium cation, cycloheptatriene base positively charged ion, there is the ferrocene cation of transition metal etc.R f～R imutually identical or different, be organic radical, be preferably aryl.）
As above-mentioned carbocation, can enumerate particularly three of triphenylcarbenium positively charged ion, three (aminomethyl phenyl) carbocation, three (3,5-dimethylphenyl) carbocation etc. and replace carbocation etc.
As above-mentioned ammonium cation, can enumerate particularly the trialkyl ammonium positively charged ion of trimethyl ammonium positively charged ion, triethyl ammonium positively charged ion, three (n-propyl) ammonium cation, triisopropyl ammonium cation, three (normal-butyl) ammonium cation, triisobutyl ammonium cation etc., N, accelerine positively charged ion, N, N-Diethyl Aniline positively charged ion, N, N-2,4, the N of 6-pentamethylaminobenzene positively charged ion etc., the dialkyl ammonium positively charged ion of N-dialkyl aniline positively charged ion, di-isopropyl ammonium cation, dicyclohexyl ammonium cation etc. etc.
As Shang Shu phosphonium cation, can enumerate particularly triphenyl phosphonium positively charged ion, three (aminomethyl phenyl) phosphonium cation, three (the San Fang Ji phosphonium cation of 3,5-dimethylphenyl) phosphonium cation etc. etc.
Among above-mentioned, as R e+, preferably carbocation, ammonium cation etc., particularly preferably triphenylcarbenium positively charged ion, DMA positively charged ion, N, N-Diethyl Aniline positively charged ion.
As carbon salt, can enumerate particularly triphenylcarbenium tetraphenyl borate salts, triphenylcarbenium four (pentafluorophenyl group) borate, triphenylcarbenium four (3,5-bis-trifluoromethyls) borate, three (4-aminomethyl phenyl) carbon four (pentafluorophenyl group) borate, three (3,5-3,5-dimethylphenyl) carbon four (pentafluorophenyl group) borates etc.
As ammonium salt, can enumerate trialkyl substituted ammonium salt, N, N-dialkyl benzene amine salt, dialkyl ammonium salt etc.
As trialkyl substituted ammonium salt, for example can enumerate particularly triethyl tetraphenyl ammonium borate, tripropyl tetraphenyl ammonium borate, three (normal-butyl) tetraphenyl ammonium borate, trimethylammonium four (p-methylphenyl) ammonium borate, trimethylammonium four (o-tolyl) ammonium borate, three (normal-butyl) four (pentafluorophenyl group) ammonium borates, triethyl four (pentafluorophenyl group) ammonium borate, tripropyl four (pentafluorophenyl group) ammonium borate, tripropyl four (2,4-3,5-dimethylphenyl) ammonium borate, three (normal-butyls) four (3,5-3,5-dimethylphenyl) ammonium borate, three (normal-butyls) four (4-trifluoromethyl) ammonium borate, three (normal-butyls) four (3,5-, bis-trifluoromethyls) ammonium borate, three (normal-butyl) four (o-tolyl) ammonium borates, octacosane ylmethyl tetraphenyl ammonium borate, octacosane ylmethyl four (p-methylphenyl) ammonium borate, octacosane ylmethyl four (o-tolyl) ammonium borate, octacosane ylmethyl four (pentafluorophenyl group) ammonium borate, octacosane ylmethyl four (2,4-3,5-dimethylphenyl) ammonium borate, octacosane ylmethyl four (3,5-3,5-dimethylphenyl) ammonium borate, octacosane ylmethyl four (4-trifluoromethyl) ammonium borate, octacosane ylmethyl four (3,5-, bis-trifluoromethyls) ammonium borate, octacosyl ammonium methyl etc.
As N, N-dialkyl benzene amine salt, for example can enumerate particularly N, accelerine tetraphenyl borate salts, N, accelerine four (pentafluorophenyl group) borate, N, accelerine four (3, 5-bis-trifluoromethyls) borate, N, N-Diethyl Aniline tetraphenyl borate salts, N, N-Diethyl Aniline four (pentafluorophenyl group) borate, N, N-Diethyl Aniline four (3, 5-bis-trifluoromethyls) borate, N, N-2, 4, 6-pentamethylaminobenzene tetraphenyl borate salts, N, N-2, 4, 6-pentamethylaminobenzene four (pentafluorophenyl group) borate etc.
As dialkyl ammonium salt, for example can enumerate particularly two (1-propyl group) four (pentafluorophenyl group) ammonium borates, dicyclohexyl tetraphenyl ammonium borate etc.
Other, also can unrestrictedly use by the disclosed ionic compound of the applicant (TOHKEMY 2004-51676 communique).
In addition, ionic compound as described above (b-2) both can use separately, also can mix two or more use.
［ organo-aluminium compound (b-3) ］
As the organo-aluminium compound (b-3) that forms olefin polymerization catalysis, for example, can enumerate the 1st family's metal and the complexing alkylide of aluminium etc. shown in the organo-aluminium compound shown in following general formula ［ 7 ］, following general formula ［ 8 ］.
R a mAl(OR b) nH pX q……［7］
(in formula, R aand R bmutually identical or different, represent the alkyl that carbonatoms is 1～15, preferably represent the alkyl that carbonatoms is 1～4, X represents halogen atom, m is the number of 0 < m≤3, and n is the number of 0≤n < 3, and p is the number of 0≤p < 3, q is the number of 0≤q < 3, and m+n+p+q=3.) shown in organo-aluminium compound.
As the object lesson of such compound, can enumerate three (alkyl) aluminium of trimethyl aluminium, triethyl aluminum, three (normal-butyl) aluminium, three (n-hexyl) aluminium, three (n-octyl) aluminium etc.; Three (branched-chain alkyl) aluminium of triisopropylaluminiuand, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three (2-methyl butyl) aluminium, three (3-methyl hexyl) aluminium, three (2-ethylhexyl) aluminium etc.; The tricyclic alkyl aluminium of thricyclohexyl aluminium, three ring octyl group aluminium etc.; The triaryl aluminum of triphenyl aluminum, trimethylphenyl aluminium etc.; The dialkyl group aluminum hydride of di-isopropyl aluminum hydride, diisobutyl aluminium hydride etc.; General formula (i-C 4h 9) xal y(C 5h 10) z(in formula, x, y, z is positive number, z≤2x.) shown in the thiazolinyl aluminium of isopentene group aluminium etc.; The aluminum alkyls alkoxide of aluminium isobutyl methylate, aluminium isobutyl ethylate etc.; The aluminum dialkyl alkoxide of dimethyl aluminium methylate, diethyl aluminum ethylate, dibutyl aluminium butanolate etc.; The aluminum alkyls sesquialter alkoxide of aluminium triethyl sesquialter ethylate, butyl aluminium sesquialter butanolate etc.; There is general formula R a 2.5al (OR b) 0.5deng shown in the oxyalkylated aluminum alkyls of part of average composition; The aluminum alkyls aromatic oxide of diethyl aluminum phenates, diethyl aluminum (2,6-di-t-butyl-4-methyl phenates) etc.; The dialkylaluminum halides of dimethylaluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride etc.; The alkyl sesquialter aluminum halide of ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, ethyl sesquialter aluminum bromide etc.; The partially halogenated aluminum alkylss such as the alkyl dihalide aluminium of ethylaluminum dichloride etc.; The dialkyl group aluminum hydride of ADEH, diisobutyl aluminium hydride etc.; Other partially hydrogenated aluminum alkylss such as the alkyl aluminum dihydride of ethyl dihydroaluminium, propyl group aluminum dihydride etc.; The aluminum alkyls of the part alkoxylates such as oxyethyl group ethylaluminium chloride, butoxy chlorinated butyl aluminium, oxyethyl group bromination aluminium triethyl and halogenation etc.
M 2AlR a 4……［8］
(in formula, M 2represent Li, Na or K, R arepresent the alkyl that carbonatoms is 1～15, preferably represent that carbonatoms is 1～4 alkyl.) shown in the periodic table of elements the 1st family's metal and the complexing alkylide of aluminium.
As the object lesson of such compound, can enumerate LiAl (C 2h 5) 4, LiAl (C 7h 15) 4deng.
In addition, also can use and compound like the compounds shown in above-mentioned general formula ［ 8 ］, for example, can enumerate the organo-aluminium compound of 2 above aluminum compounds via nitrogen-atoms combination.As such compound, can enumerate particularly (C 2h 5) 2alN (C 2h 5) Al (C 2h 5) 2deng.
From obtaining easiness aspect, as organo-aluminium compound (b-3), preferably use triethyl aluminum, triisobutyl aluminium, three (n-octyl) aluminium, diisobutyl aluminium hydride.
In addition, organo-aluminium compound as described above (b-3) both can use separately, also can mix two or more use.
In addition, the olefin polymerization catalysis using in the present invention, except transistion metal compound (A) and organometallic compound (B), can also comprise carrier (C) as required.
［ carrier (C) ］
The carrier (C) using in the present invention is inorganic or organic compound, is particulate state or microgranular solid.Wherein, as mineral compound, preferably porous oxide, butter, clay, clay mineral or ion exchangeable lamellar compound
As porous oxide, particularly can use SiO 2, Al 2o 3, MgO, ZrO, TiO 2, B 2o 3, CaO, ZnO, BaO, ThO 2deng or the mixture or the mixture that comprise them.For example, can use natural or synthetic zeolite, SiO 2-MgO, SiO 2-Al 2o 3, SiO 2-TiO 2, SiO 2-V 2o 5, SiO 2-Cr 2o 3, SiO 2-TiO 2-MgO etc.Wherein, preferably with SiO 2and/or Al 2o 3for the porous oxide of main component.Such porous oxide, its proterties is along with kind and method for making and difference, the carrier preferably using in the present invention, particle diameter is 10～300 μ m, is preferably 20～200 μ m, specific surface area is at 50～1000m 2the scope of/g, preferably at 100～700m 2the scope of/g, pore volume is wished at 0.3～3.0cm 3the scope of/g.Such carrier, fires use at 100～1000 ℃ as required, preferably fires use at 150～700 ℃.
As butter, can use MgCl 2, MgBr 2, MnCl 2, MnBr 2deng.Butter both can directly use, and after also can being pulverized by ball mill, vibration mill, used.In addition, also can use butter to be dissolved in the solvent of alcohol etc. after, make it with microgranular precipitate of separating out by precipitation agent.
The clay using in the present invention, forms take clay mineral as main component conventionally.In addition, the ion exchangeable lamellar compound using in the present invention, is to have the face being made up of ionic linkage etc. mutually with the compound of the parallel overlapping crystalline structure forming of weak binding power, and the ion containing can exchange.Most of clay mineral is ion exchangeable lamellar compound.In addition, as these clays, clay mineral, ion exchangeable lamellar compound, be not limited to natural product, also can use synthetic material.In addition, as clay, clay mineral or ion exchangeable lamellar compound, can enumerate clay, clay mineral or the tightly packed type of six sides, antimony type, CdCl 2type, CdI 2types etc. have the ionic crystal compound of layered crystal structure etc.As such clay, clay mineral, can enumerate kaolin, wilkinite, knaur clay, frog order clay, malthacite, sjogrenite, pyrophyllite, mica group, smectites, vermiculite, chlorite class, polygorskite, kaolinite, nakrite, dickite, halloysite etc., as ion exchangeable lamellar compound, can enumerate α-Zr (HAsO 4) 2h 2o, α-Zr (HPO 4) 2, α-Zr (KPO 4) 23H 2o, α-Ti (HPO 4) 2, α-Ti (HAsO 4) 2h 2o, α-Sn (HPO 4) 2h 2o, γ-Zr (HPO 4) 2, γ-Ti (HPO 4) 2, γ-Ti (NH 4pO 4) 2h 2the crystallinity acid-salt of the polyvalent metals such as O etc.Also preferably the clay using in the present invention, clay mineral are applied to chemical treatment.As chemical treatment, can use and remove the processing that impacts in the surface treatment of the impurity of surface attachment, to the crystalline structure of clay etc.As chemical treatment, can enumerate particularly acid treatment, alkaline purification, salt processing, organism processing etc.
The ion exchangeable lamellar compound using in the present invention can be to utilize ion exchangeable, by by the exchangeability ion of interlayer and other bulky ion-exchange and the lamellar compound of the state of interlayer expansion.Bulky ion is like this born the effect of the pillar of supporting laminate structure, is commonly referred to column form object (Pillar).In addition, the interlayer at lamellar compound is like this imported to other materials and be called embedding.As the guest compound embedding, can enumerate TiCl 4, ZrCl 4etc. cationic mineral compound, Ti (OR) 4, Zr (OR) 4, PO (OR) 3, B (OR) 3deng metal alkoxide (R is alkyl etc.), ［ Al 13o 4(OH) 24? 7+, ［ Zr 4(OH) 14? 2+, ［ Fe 3o (OCOCH 3) 6? +deng metal hydroxides ion.Two or more use alone or in combination of these compounds.In addition, in the time embedding these compounds, also can make to be hydrolyzed Si (OR) 4, Al (OR) 3, Ge (OR) 4deng metal alkoxide (R is alkyl etc.) polymkeric substance, the SiO that obtain 2isocolloid shape mineral compound coexists.In addition, as column form object, can be set forth in oxide compound being generated by thermal dehydration after the above-mentioned metal hydroxides ion of intercalation etc.Wherein, be preferably clay or clay mineral, be particularly preferably montmorillonite, vermiculite, stellite, taincolite and synthetic mica.
As the organic compound of carrier (C), can enumerate particulate state or the microgranular solid of particle diameter in 10～300 μ m scopes.The alpha-olefin that can to enumerate using carbonatomss such as ethene, propylene, 1-butylene, 4-methyl-1-pentenes be particularly 2～14 is as (copolymerization) polymkeric substance that main component was generated, with vinyl cyclohexane, vinylbenzene for (copolymerization) polymkeric substance that main component was generated and their modifier.
In addition, carrier as described above (C) both can use separately, also can mix two or more use.
In addition, the olefin polymerization catalysis using in the present invention, except the carrier (C) of transistion metal compound (A), organometallic compound composition (B) and use as required, can also include organic compounds (D).
［ organic compound (D) ］
In the present invention use organic compound (D), as required, for make polymerization and generation polymkeric substance physical property improve object and use.As such organic compound, can enumerate alcohols, phenoloid, carboxylic acid, phosphorus compound and sulfonate etc., but be not limited to this.
In addition, organic compound as described above (D) both can use separately, also can mix two or more use.
In the time of polymerization, using method, the order of addition of mentioned component are selected arbitrarily, the method that can be listed below.
(1) independent method of adding transistion metal compound (A) in polymerizer.
(2) in polymerizer, add transistion metal compound (A) and the method for organometallic compound (B) with random order.
(3) in polymerizer, be added on the catalyst component that is carried with transistion metal compound (A) on carrier (C), the method for organometallic compound (B) with random order.
(4) in polymerizer, be added on the catalyst component that is carried with organometallic compound (B) on carrier (C), the method for transistion metal compound (A) with random order.
(5) in polymerizer, be added on the method that is carried with the catalyst component of transistion metal compound (A) and organometallic compound (B) on carrier (C).
In the method for above-mentioned (1)～(5), organic compound (D) can add with random order in polymerizer, in addition, adds after also can making in advance it contact in advance with the more than at least a kind composition in (A)～(C) in polymerizer.In addition, in the method for above-mentioned (2)～(5), catalyst component at least two or more can contact in advance.
In the method for above-mentioned (4) that hold organometallic compound (B), (5), as required, also can add the organometallic compound (B) not held with random order.Now, organometallic compound (B) both can be the same or different.
In addition, on composition (C), be carried with the solid catalyst component of transistion metal compound (A), on composition (C), be carried with the solid catalyst component of transistion metal compound (A) and organometallic compound (B), both can prepolymerization alkene, also can on by prepolymerized solid catalyst component, hold again catalyst component.
In the manufacture method of olefin polymer of the present invention, under the existence of catalyst for olefines polymerizing as described above, the alpha-olefin and the ethene that are 3～10 by polymerization carbonatoms obtain alpha-olefinic polymer.
< alpha-olefin >
The carbonatoms that can use is in the present invention 3～10 alpha-olefin, for example, can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene etc.Wherein, the alpha-olefin that preferably carbonatoms is 3～8, the alpha-olefin that more preferably carbonatoms is 3～6, is particularly preferably propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene.
In addition, the alpha-olefin that these carbonatomss are 3～10 can use separately a kind or combine two or more use.About the selection of alpha-olefin, can suitably select so that reach optimum in the polymer property generating.As select 1 example, for make this polymkeric substance of sulfidizing or comprise this polymkeric substance mixture time physical property reach expected value etc.
The manufacture method > of < olefin polymer
The present invention also can implement according to any a kind of method in the liquid polymerization of solution polymerization, suspension polymerization etc. or gaseous polymerization.
As the unreactive hydrocarbons medium (unreactive hydrocarbons solvent) using, can enumerate particularly the aliphatic hydrocarbon of propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, ethylene chloride, methylene dichloride, kerosene etc. in liquid polymerization; The ester ring type hydrocarbon of pentamethylene, hexanaphthene, methylcyclopentane etc.; The aromatic hydrocarbons of benzene, toluene, chlorobenzene, dimethylbenzene etc.; Or their mixture.In addition, also can use alpha-olefin itself as solvent.
Use catalyst for olefines polymerizing as described above, in the time carrying out the polymerization of alkene, every 1 liter of reaction volume, transistion metal compound (A) is conventionally with 10 -9～10 -1mole, preferably with 10 -8～10 -2mole amount use.
Organoaluminoxy compound (b-1) with transistion metal compound (A) in the mol ratio ［ (b-1)/M ］ of whole transition metal atoms (M) be generally 0.01～50000,0.05～2000 the amount of being preferably uses.Ionic compound (b-2) is generally 0.01～50000, is preferably 0.05～2000 amount use with the mol ratio ［ (b-2)/M ］ of the transition metal atoms (M) in ionic compound (b-2) and transistion metal compound (A).Organo-aluminium compound (b-3) is generally 0.01～5000, is preferably 0.05～2000 amount use with the mol ratio ［ (b-3)/M ］ of the whole transition metal (M) in the aluminium atom in organo-aluminium compound (b-3) and transistion metal compound (A).
In addition, use the polymerization temperature of the alkene of such olefin polymerization catalysis to be generally+25～+ 200 ℃, be preferably+scope of 25～+ 170 ℃ the scope of more preferably+30～+ 150 ℃.Determine according to the polymerization activity of the molecular weight of the alpha-olefinic polymer obtaining, olefin polymerization catalysis, but from the viewpoint of productivity, be preferably+more than 30 ℃.
Polymerization pressure is normally in normal pressure～10MPa gauge pressure, preferably under the condition of normal pressure～5MPa gauge pressure, and polyreaction can be carried out with any a kind of method in intermittent type, semi continuous, continous way.Polymerization can also be divided into the 2 different stages of reaction conditions carries out above.
The molecular weight of the olefin polymer obtaining also can be by hydrogen is existed in paradigmatic system, or polymerization temperature variations is regulated.While adding hydrogen, its amount is preferably every 1kg alkene 0.001～100NL left and right.In addition, also can be regulated by the amount of the composition using (B).Now, composition (B) can be enumerated triisobutyl aluminium, methylaluminoxane, zinc ethyl etc. particularly.
In the manufacture method of olefin polymer of the present invention, it is characterized in that, the ethene feed rate in polymerization reaction system is limited in to certain specified amount, determine as follows.First, at the alpha-olefin that is 3～10 using carbonatoms, when gas is supplied with, the alpha-olefin that ethene and carbonatoms are 3～10 both can have been distinguished continuously and supplied with in polymerizer, also can supply with off and on.In addition, the mole number of the ethene of supplying with polymerizer is made as to P e, the mole number of the alpha-olefin that is 3～10 by carbonatoms is made as P otime, be all dissolved in liquid as prerequisite because ethene feed rate is small take the ethene of supplying with, the molar fraction P in regulation liquid e/ P o.Now, with 0.001≤P e/ P o≤ 0.030 is feature, and this scope if, just can be used arbitrarily, but is preferably 0.001≤P e/ P o≤ 0.020, more preferably 0.001≤P e/ P o≤ 0.010, most preferably be 0.001≤P e/ P o≤ 0.005.
On the other hand, the alpha-olefin that is 3～10 using carbonatoms during as liquid supply, is made as P by the mole number of the ethene of supplying with polymerizer e, the mole number of the alpha-olefin that is 3～10 by carbonatoms is made as P otime, be dissolved in the alpha-olefin of carbonatoms as 3～10 as prerequisite take the ethene of supplying with, the molar fraction P in regulation liquid e/ P o.Now, with 0.001≤P e/ P o≤ 0.030 is feature, and this scope if, just can be used arbitrarily, but is preferably 0.001≤P e/ P o≤ 0.020, more preferably 0.001≤P e/ P o≤ 0.010, most preferably be 0.001≤P e/ P o≤ 0.005.
In the manufacture method of olefin polymer of the present invention, the degree that improves effect by the molecular weight with performance polymerization activity and alpha-olefinic polymer makes micro-vinyl polymerization, just can manufacture dystectic syndiotaktisch isotactic alpha-olefin propylene series copolymer.As mentioned above, known in the time of metallocene catalyst polymerisation propylene, exist propylene to react with the state of 2,1-insertion the catalyzer kind stopping, when alpha-olefin that can to think at polymerization carbonatoms be 3～10, also there is the catalyzer kind that becomes similar halted state.Wherein, can think if make the ethylene reaction of specified amount above, the catalyzer kind reactivate of halted state not only can be made to active raising, and can suppress the disengaging of polymer chain from catalyzer kind, therefore can make the growth response of the polymer chain temporarily stopping again starting, its result, the molecular weight of alpha-olefinic polymer increases.In addition, unexpectedly, than manufacturing isotaxy alpha-olefinic polymer, it is characterized in that, in the time manufacturing syndiotaktisch isotactic alpha-olefin propylene series copolymer, can see the effect significantly improving.
< olefin polymer >
Then, the olefin polymer being obtained by manufacture method of the present invention is described.The olefin polymer of being manufactured by manufacture method of the present invention has following 4 features.
［ feature 1 ］
It is to comprise to be derived from that to be selected from carbonatoms be at least a kind of above structural unit X of alpha-olefin in 3～10 alpha-olefin and the polymkeric substance of the structural unit Y of derived from ethylene, it is characterized in that, the content of the structural unit X occupying is made as to x(mol%) in polymkeric substance, the content of the structural unit Y occupying in polymkeric substance is made as to y(mol%) time, 98.5≤x≤99.9 and 1.5 >=y >=0.1, and x+y=100, be preferably 98.6≤x≤99.9 and 1.4 >=y >=0.1, and x+y=100, more preferably 98.7≤x≤99.9 and 1.3 >=y >=0.1, and x+y=100, most preferably be 98.8≤x≤99.9 and 1.2 >=y >=0.1, and x+y=100.The olefin polymer of being manufactured by manufacture method of the present invention, although the unit that comprises micro-derived from ethylene is also maintaining high racemize diad point rate, high-melting-point, molecular weight also improves.When ethylene content y in olefin polymer is greater than specialized range, because the melting point depression of olefin polymer not only, and Tc (Tc) also declines, so forming process may worsen.
［ feature 2 ］
With by 13the racemize diad point rate (［ r ］) that C-NMR measures is that 90%≤［ r ］ < 100% is feature, be preferably 95%≤［ r ］ < 100%, more preferably 97%≤［ r ］ < 100%, most preferably is 98%≤［ r ］ < 100%.The olefin polymer of being manufactured by manufacture method of the present invention, because racemize diad divides rate high, so although the unit that comprises micro-derived from ethylene is also maintaining high-melting-point.
［ feature 3 ］
The limiting viscosity (［ η ］) recording take the naphthane solution by 135 ℃ is as 0.70dl/g is above as feature.More than being preferably 0.75dl/g, more preferably more than 0.80dl/g, more than most preferably being 0.85dl/g.The olefin polymer that molecular weight is high can expect to show good intensity and forming process.
［ feature 4 ］
Be preferably Tm >=147 ℃ as feature above take the fusing point (Tm) obtained by differential scanning calorimeter (DSC) as 145 ℃, more preferably Tm >=149 ℃, most preferably are Tm >=151 ℃.The olefin polymer of being manufactured by manufacture method of the present invention, although the unit that comprises micro-derived from ethylene is also maintaining high racemize diad point rate, high-melting-point, molecular weight also improves.
Olefin polymer of the present invention, although the unit that comprises micro-derived from ethylene is also maintaining high racemize diad point rate, high-melting-point, molecular weight is also high, can think that this is because the arrangement of alpha-olefin is syndiotactic cause.As the feature of syndiotactic structure, knownly can take as mentioned above stable crystalline structure on multiple energy such as spirane structure, planar zigzag structure, can also reversibly phase transition between a part of crystalline structure.When isotactic polyprophlene, the position because the spirane structure rotating 1 week with 3 molecule propylene is had the advantage, so while containing therein the unit of micro-derived from ethylene, can produce large impact to the crystalline structure forming, fusing point easily declines, with respect to this, in the time of syndiotactic polypropylenes, infer that the impact that by taking crystalline structure stable on multiple energy, the unit of derived from ethylene is given to crystalline structure minimizes, as its result, fusing point becomes and is difficult to decline.In addition, because the syndiotaktisch isotactic alpha-olefin propylene series copolymer of same effect beyond propylene is also visible, so can think that this is characteristic phenomenon in syndiotactic structure.
Embodiment
Below, based on embodiment, be described more specifically the present invention, but the present invention is not limited by these embodiment.First, the method for the physical property of measuring the olefin polymer being obtained by manufacture method of the present invention is described.
< limiting viscosity ［ η ］ >
It is for using naphthane solvent 135 ℃ of values that record.
< fusing point (Tm), Tc (Tc), melting heat (Δ H(Tm)) >
For 4-methyl-1-pentene polymkeric substance, the differential scanning calorimeter EXSTAR6000DSC that uses Seiko electronics nanosecond science and technology Co., Ltd. (SIINanoTechnology Inc.) to produce, under stream of nitrogen gas (20mL/min), with 10 ℃/min, sample (about 5mg) is warmed up to 270 ℃, keep after 5 minutes at 270 ℃, be cooled to 0 ℃ with-10 ℃/min, keep, after 5 minutes, being warmed up to 270 ℃ with 10 ℃/min at 0 ℃.The summit at the Tc peak during using now cooling is as Tc (Tc).In addition, the summit of the crystallization melting peak during using the 2nd intensification, as fusing point (Tm), calculates melting heat (Δ H(Tm) from the integrating value at peak).
For propene polymer, the differential scanning calorimeter EXSTAR6000DSC that uses Seiko electronics nanosecond science and technology Co., Ltd. to produce, under stream of nitrogen gas (20mL/min), with 10 ℃/min, sample (about 5mg) is warmed up to 230 ℃, keep after 10 minutes at 230 ℃, be cooled to 30 ℃ with-10 ℃/min, keep, after 5 minutes, being warmed up to 230 ℃ with 10 ℃/min at 30 ℃.The summit at the Tc peak during using now cooling is as Tc (Tc).In addition, the summit of the crystallization melting peak during using the 2nd intensification, as fusing point (Tm), calculates melting heat (Δ H(Tm) from the integrating value at peak).
In addition, in the olefin polymer that embodiment and comparative example obtain, while observing 2 above crystallization melting peaks, the summit at the peak of peak melting point side is defined as to the fusing point (Tm) of olefin polymer.
< taxis and ethylene content >
With orthodichlorobenzene-d 4/ benzene-d 6(4/1 ［ v/v ］) and sym.-tetrachloroethane-d 2for measuring solvent, by measuring 120 ℃ of mensuration of temperature 13c-NMR spectrum (125MHz, NEC produce ECP500 type and 100MHz, NEC are produced ECX400P type) calculates the racemize diad point rate (［ r ］) of olefin polymer.Wherein, the impact of ignoring ethylene insertion is calculated.For example, about the polymkeric substance take 4-methyl-1-pentene as main component, if near the integrated value of the signal from racemize structure (42.7ppm) is made as to A, near the integrated value of the signal from meso structure (42.4ppm) is made as to B, calculates as meso diad point rate (［ m ］)/racemize diad point rate (［ r ］)=B/A and ［ m ］+［ r ］=100.About the polymkeric substance take propylene as main component, can calculate with reference to known document.In addition ethylene content by 13c-NMR spectrum, obtains with reference to (Macromolecules, 1982,15,1150).
< molar fraction >
In the alpha-olefin that is 3～10 at carbonatoms, use the situation of propylene exemplified as the example of gas, use the situation of 4-methyl-1-pentene exemplified as the example of liquid.As mentioned above, in the situation of propylene, the mole number of the ethene of supply is made as to M e, the mole number of the propylene of supply is made as to M o, as molar fraction M e/ M o=(ethene flow/propylene flow) calculates.In addition, in the situation of 4-methyl-1-pentene, the mole number of the ethene of supply is made as to P e, the mole number of 4-methyl-1-pentene is made as to P o, as molar fraction P e/ P o=(add-on of ethene flow/4-methyl-1-pentene) calculates.
< transistion metal compound (A) >
Transistion metal compound (A) is synthetic with the method for recording in following Japanese patent gazette.TOHKEMY 2000-212194 communique, TOHKEMY 2004-168744 communique, TOHKEMY 2004-189666 communique, TOHKEMY 2004-161957 communique, TOHKEMY 2007-302854 communique, TOHKEMY 2007-302853 communique, WO01/027124 communique, Japanese Unexamined Patent Application Publication 2001-526730 communique, Japanese kokai publication hei 10-226694 communique.
Transistion metal compound (a1): dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride
Figure BDA00001784774300251
Transistion metal compound (a2): dibenzyl methylene radical (cyclopentadienyl) (2,7-, bis-rubigan-3,6-di-t-butyl fluorenyl) zirconium dichloride
Figure BDA00001784774300252
Transistion metal compound (a3): phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride
Transistion metal compound (a4): dibenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Figure BDA00001784774300262
Transistion metal compound (a5): two p-chlorobenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Figure BDA00001784774300263
［ embodiment 1 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 30 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.79mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of nitrogen 2.5NL/h, ethene 0.5NL/h is circulated, start polymerization.Because the P in polymerization atmosphere o=1.5875, P e=0.0037, so calculate P e/ P o=0.0023.The mixed gas of nitrogen and ethene in polymerization also continuously supply with, under normal pressure, 30 ℃ carry out, after polymerization in 10 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 4.90g.Polymerization activity is 7.35kg/mmol-Zrhr, ［ η ］=0.88dl/g, the Tc=153 of the 4-methyl-1-pentene polymkeric substance obtaining ℃, Tm=201 ℃, Δ H(Tm)=14.2mJ/mg, ethylene content=0.2%, ［ r ］=98.2%.
［ embodiment 2 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 30 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.79mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of nitrogen 10NL/h, ethene 2NL/h is circulated, start polymerization.P in polymerization atmosphere o=1.5875, P e=0.0074, calculate P e/ P o=0.0047.The mixed gas of nitrogen and ethene in polymerization also continuously supply with, under normal pressure, 30 ℃ carry out, after polymerization in 5 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 2.59g.Polymerization activity is 7.77kg/mmol-Zrhr, the limiting viscosity ［ η ］ of the 4-methyl-1-pentene polymkeric substance obtaining=0.98dl/g, Tc=149 ℃, Tm=199 ℃, Δ H(Tm)=15.1mJ/mg, ethylene content=0.4%, ［ r ］=97.7%.
［ embodiment 3 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 30 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.79mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of nitrogen 10NL/h, ethene 6NL/h is circulated, start polymerization.P in polymerization atmosphere o=1.5875, P e=0.0223, calculate P e/ P o=0.0141.The mixed gas of nitrogen and ethene in polymerization also continuously supply with, under normal pressure, 30 ℃ carry out, after polymerization in 5 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 2.96g.Polymerization activity is 8.88kg/mmol-Zrhr, the limiting viscosity ［ η ］ of the 4-methyl-1-pentene polymkeric substance obtaining=1.10dl/g, Tc=143 ℃, Tm=197 ℃, Δ H(Tm)=13.7mJ/mg, ethylene content=0.6%, ［ r ］=97.6%.
［ embodiment 4 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 30 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.79mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of nitrogen 10NL/h, ethene 10NL/h is circulated, start polymerization.As the P in polymerization atmosphere o=1.5875, P emole number=0.0372 of=ethene, calculates P e/ P o=0.0234.The mixed gas of nitrogen and ethene in polymerization also continuously supply with, under normal pressure, 30 ℃ carry out, after polymerization in 5 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 3.18g.Polymerization activity is 9.54kg/mmol-Zrhr, the limiting viscosity ［ η ］ of the 4-methyl-1-pentene polymkeric substance obtaining=1.18dl/g, Tc=139 ℃, Tm=195 ℃, Δ H(Tm)=12.7mJ/mg, ethylene content=1.0%, ［ r ］=97.9%.
［ comparative example 1 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 30 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.79mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system and make nitrogen 50NL/h circulation, start polymerization.Nitrogen in polymerization also continuously supply with, under normal pressure, 30 ℃ carry out, after polymerization in 30 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 0.43g.Polymerization activity is 0.22kg/mmol-Zrhr, the limiting viscosity ［ η ］ of the 4-methyl-1-pentene polymkeric substance obtaining=0.60dl/g, Tc=155 ℃, Tm=204 ℃, Δ H(Tm)=20.3mJ/mg, ethylene content=0.0%, ［ r ］=98.0%.
［ comparative example 2 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
Be blown into pipe from glass system the mixed gas of nitrogen 10NL/h, ethene 100NL/h is circulated, the P in polymerization atmosphere e/ P o=0.2340, in addition, test according to embodiment 1.
［ comparative example 3 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
Be blown into pipe from glass system the mixed gas of ethene 150NL/h is circulated, the P in polymerization atmosphere e/ P o=0.2808, in addition, test according to embodiment 1.
［ embodiment 5 ］
［ manufacture of propene polymer ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 400mL heptane, remain on 50 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 2.62mL(A1=4mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 3.67mg(0.004mmol) dibenzyl methylene radical (cyclopentadienyl) (2,7-bis-rubigan-3,6-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of propylene 150NL/h, ethene 1NL/h is circulated, start polymerization.Calculate the P in polymerization atmosphere e/ P o=0.0067.Propylene/ethylene mixed gas in polymerization also continuously supply with, under normal pressure, 50 ℃ carry out, after polymerization in 15 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, propene polymer is separated out.The propene polymer obtaining carries out 10 hours drying under reduced pressure at 80 ℃, and result obtains 3.76g propene polymer.Polymerization activity is 3.76kg/mmol-Zrhr, ［ η ］=1.57dl/g, the Tc=102 of the propene polymer obtaining ℃, Tm=155 ℃, Δ H(Tm)=51.6mJ/mg, ethylene content=0.5%, ［ r ］=98.0%.
［ embodiment 6 ］
［ manufacture of propene polymer ］
Be blown into pipe from glass system the mixed gas of propylene 150NL/h, ethene 0.8NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0053, in addition, test according to embodiment 5.
［ embodiment 7 ］
［ manufacture of propene polymer ］
Be blown into pipe from glass system the mixed gas of propylene 150NL/h, ethene 1.5NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0100, in addition, test according to embodiment 5.
［ embodiment 8 ］
［ manufacture of propene polymer ］
Be blown into pipe from glass system the mixed gas of propylene 150NL/h, ethene 4.0NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0267, in addition, test according to embodiment 5.
［ comparative example 4 ］
［ manufacture of propene polymer ］
Be blown into pipe from glass system and only make propylene 150NL/h circulation, start polymerization, in addition, test according to embodiment 5.
［ comparative example 5 ］
［ manufacture of propene polymer ］
Be blown into pipe from glass system the mixed gas of propylene 150NL/h, ethene 10.5NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0700, in addition, test according to embodiment 5.
［ embodiment 9 ］
［ manufacture of propene polymer ］
Transistion metal compound is made as (a4): dibenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, being blown into pipe from glass system circulates the mixed gas of propylene 150NL/h, ethene 0.3NL/h, start polymerization, the P in polymerization atmosphere e/ P o=0.0020, in addition, test according to embodiment 5.
［ embodiment 10 ］
［ manufacture of propene polymer ］
Transistion metal compound is made as (a4): dibenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, in addition, test according to embodiment 5.
［ comparative example 6 ］
［ manufacture of propene polymer ］
Transistion metal compound is made as (a4): dibenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, be blown into pipe from glass system and only make propylene 150NL/h circulation, start polymerization, in addition, test according to embodiment 5.
［ embodiment 11 ］
［ manufacture of propene polymer ］
Transistion metal compound is made as (a5): two p-chlorobenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, being blown into pipe from glass system circulates the mixed gas of propylene 150NL/h, ethene 0.45NL/h, start polymerization, the P in polymerization atmosphere e/ P o=0.0033, in addition, test according to embodiment 5.
［ comparative example 7 ］
［ manufacture of propene polymer ］
Transistion metal compound is made as (a5): two p-chlorobenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, be blown into pipe from glass system and only make the circulation of 150NL/h propylene, start polymerization, in addition, test according to embodiment 5.
［ reference example 1 ］
［ manufacture of 4-methyl-1-pentene polymkeric substance ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 40 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.96mg(0.004mmol) phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system and make nitrogen 25NL/h circulation, start polymerization.Nitrogen in polymerization also continuously supply with, under normal pressure, 40 ℃ carry out, after polymerization in 30 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 1.82g.Polymerization activity is 0.91kg/mmol-Zrhr, the limiting viscosity ［ η ］ of the 4-methyl-1-pentene polymkeric substance obtaining=2.04dl/g, Tc=203 ℃, Tm=232 ℃, Δ H(Tm)=27.8mJ/mg, ethylene content=0.0%, ［ r ］=2.0%.
［ reference example 2 ］
In the glass autoclave processed (being blown into pipe with glass system) of the inner capacities 500mL fully replacing at nitrogen, add 4-methyl-1-pentene 200mL, remain on 40 ℃.On the other hand, in the side-tube flask of the inner capacities 30mL fully replacing at nitrogen, add magnetic stir bar, add therein 1.31mL(A1=2mmol) hexane solution (A1 concentration: 1.52mol/L) of methylaluminoxane produced of Tosoh-finechem, then, add 2.96mg(0.004mmol) phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stir 10 minutes.In the autoclave that makes in advance nitrogen circulation, add the toluene solution (A1=1.0M) of 1.0mmol triisobutyl aluminium, then, in autoclave, add above-mentioned solution, be blown into pipe from glass system the mixed gas of nitrogen 100NL/h, ethene 20NL/h is circulated, start polymerization.As the P in polymerization atmosphere o=1.5875, P e=0.1488, calculate P e/ P o=0.0937.Nitrogen/ethene mixed gas in polymerization also continuously supply with, under normal pressure, 40 ℃ carry out, after polymerization in 10 minutes, adding a small amount of isopropylcarbinol and stopping polymerization.In the 1.5L methyl alcohol that comprises 1mL hydrochloric acid, add polymers soln, 4-methyl-1-pentene polymkeric substance is separated out.It is carried out to 10 hours drying under reduced pressure at 80 ℃, and result obtains 4-methyl-1-pentene polymkeric substance 1.03g.Polymerization activity is 1.55kg/mmol-Zrhr, ［ η ］=1.57dl/g, the Tc=200 of the 4-methyl-1-pentene polymkeric substance obtaining ℃, Tm=228 ℃, Δ H(Tm)=19.2mJ/mg, ethylene content=0.3%, ［ r ］=2.0%.
［ reference example 3 ］
Be blown into pipe from glass system the mixed gas of nitrogen 25NL/h, ethene 0.5NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0023, in addition, test according to reference example 2.
［ reference example 4 ］
Be blown into pipe from glass system the mixed gas of nitrogen 20NL/h, ethene 4NL/h is circulated, start polymerization, the P in polymerization atmosphere e/ P o=0.0190, in addition, test according to reference example 2.
In table 1-1～table 1-5, represent the result of embodiment 1～11, comparative example 1～7, reference example 1～4.
［ table 1-1 ］
Figure BDA00001784774300331
［ table 1-2 ］
［ table 1-3 ］
Figure BDA00001784774300342
［ table 1-4 ］
Figure BDA00001784774300343
［ table 1-5 ］
Figure BDA00001784774300344
Transistion metal compound:
A1: dibenzyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride
A2: dibenzyl methylene radical (cyclopentadienyl) (2,7-, bis-rubigan-3,6-di-t-butyl fluorenyl) zirconium dichloride
A3: phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride
A4: dibenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
A5: two p-chlorobenzyl methylene radical (cyclopentadienyl) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Industrial utilizability
By the present invention, under the industrial condition that can manufacture, can, with excellent polymerization activity, manufacture high molecular and dystectic syndiotaktisch isotactic alpha-olefin propylene series copolymer, the contribution that this fact gives polyolefin industry circle is very large.For example, using propylene and ethene when monomer uses, although the unit that the syndiotactic polypropylenes obtaining comprises micro-derived from ethylene, racemize diad divides rate, molecular weight all high, is maintaining high-melting-point.In addition, while using the alpha-olefin beyond propylene, be that can to manufacture racemize diad point rate, molecular weight all high and maintain the method that dystectic syndiotaktisch isotactic alpha-olefin propylene series copolymer etc. can widespread use industrial similarly, be highly profitable.

Claims (12)

1. a manufacture method for syndiotaktisch isotactic alpha-olefin propylene series copolymer, is characterized in that:
Comprising the transistion metal compound shown in (A) following general formula ［ 1 ］ and (B) be selected from the right compound of (b-2) and transistion metal compound (A) reacting forming ion and (b-3) under the existence of the catalyst for olefines polymerizing of at least a kind of compound in organo-aluminium compound, when the monomer of the alpha-olefin that under the condition at polymerization temperature more than 25 ℃, aggregate packet is 3～10 containing more than a kind carbonatoms and a small amount of ethene, the ethene mole number of supply polymerizer is made as to P e, the alpha-olefin mole number that is 3～10 by carbonatoms is made as P otime, meet 0.001≤P e/ P o≤ 0.030,
Described polymkeric substance comprises that to be derived from carbonatoms be at least a kind of above structural unit X in 3～10 alpha-olefin and the structural unit Y of derived from ethylene, meets whole following conditions ［ 1 ］～［ 4 ］:
［ 1 ］ content of the structural unit X occupying is made as to x in polymkeric substance, unit is mol%, when the content of the structural unit Y occupying in polymkeric substance is made as to y, unit and is mol%, 98.5≤x≤99.9 and 1.5 >=y >=0.1, and x+y=100;
［ 2 ］ by 13the racemize diad point rate (［ r ］) that C-NMR measures is 90%≤［ r ］ < 100%;
［ 3 ］ limiting viscosity (［ η ］) recording take the naphthane solution of 135 ℃ is more than 0.70dl/g;
［ 4 ］ fusing point (Tm) of being obtained by differential scanning calorimeter (DSC) is more than 145 ℃,
Figure FDA0000472363630000011
In general formula ［ 1 ］, R 1, R 2, R 3and R 44 groups be selected from hydrogen atom, alkyl and containing silica-based, identical or different respectively, R 1and R 2do not mutually combine and form ring, R 3and R 4do not mutually combine and form ring, R 5and R 6for being selected from alkyl that hydrogen atom, carbonatoms are 2～20 and containing atom or substituting group in silica-based, mutually identical or different, M is selected from titanium atom, zirconium atom and hafnium atom, Q represents that halogen atom, alkyl, carbonatoms are neutral conjugated diolefine below 10 or non-conjugated diene, anion binding base or can be with the neutral dentate of lone-pair electron coordination, j represents 1～4 integer, j is 2 when above, and multiple Q are mutually identical or different.
2. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that: described (b-3) organo-aluminium compound is (b-1) Organoaluminoxy compound.
3. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that: in described general formula ［ 1 ］, and R 2and R 3for same atoms or identical group.
4. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that: in described general formula ［ 1 ］, and R 2and R 3for the tertiary butyl.
5. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that:
In described general formula ［ 1 ］, R 2and R 3for the tertiary butyl, R 1and R 4for the aryl that hydrogen atom or carbonatoms are 6～20, identical or different respectively.
6. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that: in described general formula ［ 1 ］, and R 5and R 6for the alkyl that carbonatoms is 6～20, identical or different respectively.
7. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that:
In described general formula ［ 1 ］, R 5and R 6for the aralkyl that the carbonatoms aryl that is 6～20 or carbonatoms are 6～20, identical or different respectively.
8. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 1, is characterized in that:
In described general formula ［ 1 ］, R 2and R 3for the tertiary butyl, R 1and R 4for the aryl that hydrogen atom or carbonatoms are 6～20, identical or different respectively, R 5and R 6for the aralkyl that the carbonatoms aryl that is 6～20 or carbonatoms are 6～20, identical or different respectively.
9. the manufacture method of syndiotaktisch isotactic alpha-olefin propylene series copolymer as claimed in claim 8, is characterized in that: in described general formula ［ 1 ］, and R 5and R 6for the carbonatoms aralkyl that is 6～20.
10. the manufacture method of the syndiotaktisch isotactic alpha-olefin propylene series copolymer as described in any one in claim 1～9, is characterized in that:
Described carbonatoms is that at least a kind in 3～10 alpha-olefin is propylene.
The manufacture method of 11. 1 kinds of syndiotaktisch isotactic alpha-olefin propylene series copolymers, is characterized in that:
According to manufacture method claimed in claim 1, in polymerizer, supply with ethene and/or propylene continuously or off and on, the mole number of ethene is made as to P e, the mole number of propylene is made as to P otime, 0.001≤P e/ P o≤ 0.030.
The manufacture method of 12. syndiotaktisch isotactic alpha-olefin propylene series copolymers as described in any one in claim 1～9 or 11, is characterized in that: at least a kind in the alpha-olefin that described carbonatoms is 3～10 is 4-methyl-1-pentene.
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